EP4019617A1 - Detergent composition for liquid carbon dioxide based cleaning - Google Patents

Detergent composition for liquid carbon dioxide based cleaning Download PDF

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Publication number
EP4019617A1
EP4019617A1 EP21217805.7A EP21217805A EP4019617A1 EP 4019617 A1 EP4019617 A1 EP 4019617A1 EP 21217805 A EP21217805 A EP 21217805A EP 4019617 A1 EP4019617 A1 EP 4019617A1
Authority
EP
European Patent Office
Prior art keywords
carbon dioxide
composition
liquid carbon
cleaning
chemical formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21217805.7A
Other languages
German (de)
French (fr)
Inventor
Jongseok Lee
Hee Yeon Kim
Myunghun Im
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Electronics Inc
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LG Electronics Inc
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Filing date
Publication date
Application filed by LG Electronics Inc filed Critical LG Electronics Inc
Publication of EP4019617A1 publication Critical patent/EP4019617A1/en
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43Solvents
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2068Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/20Organic compounds containing oxygen
    • C11D3/2093Esters; Carbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/24Organic compounds containing halogen
    • C11D3/245Organic compounds containing halogen containing fluorine
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50Solvents
    • C11D7/5004Organic solvents
    • C11D7/5018Halogenated solvents
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L1/00Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • C11D2111/12
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/263Ethers
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • C11D7/26Organic compounds containing oxygen
    • C11D7/266Esters or carbonates

Definitions

  • the present invention relates to a detergent composition excellent in usability for liquid carbon dioxide based cleaning.
  • washing that is a process for eliminating dirt or contaminants from textile or clothes may be divided into two categories.
  • a surfactant may be dissolved in water and the alkalinity of water may increase to remove dirt or contaminants from textile or clothes.
  • the fabric or clothes may be rinsed, and dehydrated and dried. That is a normal washing method and usually uses a laundry detergent.
  • the second washing method may remove oily contaminants from fabric (e.g., wool, silk and other natural protein fiber, artificial silk fiber and acetate fiber) by means of petroleum-based, chlorine-based, glycol ester-based, cyclic silicone, silicone-based fluorine-based, terpene oil-based such as limonene (hereinafter, 'solvent').
  • fabric e.g., wool, silk and other natural protein fiber, artificial silk fiber and acetate fiber
  • the fabric may be fiver that generates deformation in a surface and inside to lose luster, and deformation such as contraction or relaxation.
  • the second method may remove the solvent from the clothes or fabric based on a physical method and dry them to volatilize the solvent. That second washing method may be usually called 'dry cleaning'.
  • the first washing method using a typical laundry detergent may require much water. Because of that, the first washing method has an excellent effect in removing watery contaminants but a limit to the removal of oily contaminants.
  • fabric surface and fiber inside may be deformed by the alkaline washing conditions and long-term contact with water. Accordingly, luster of fibers could be lost and contraction or relaxation of fibers could occur disadvantageously.
  • neutral liquid detergents are commercially available to prevent the clothing damage or deformation caused by detergent bases.
  • neutral liquid detergents are also used by diluting in water and still have a disadvantage in that the deformation by means of water cannot be alleviated.
  • the dry cleaning method has an excellent effect in removing oily contaminants.
  • the dry cleaning uses substances that are categorized into the ones harmful to human body and environment or raw materials with poor flammability and poor polymer stability. Because of that, the raw materials used in the dry cleaning might cause malfunction of washing equipment and a fire.
  • the liquid carbon dioxide-based cleaning may wash, rinse and dry various types of clothes by means of phase change characteristics between gas and liquid of carbon dioxide quickly and without damage, and remove contaminant remnants from the clothes.
  • liquid carbon dioxide may wash and rinse clothes at high pressure.
  • Liquid carbon dioxide contained in the laundry may be vaporized quickly at low pressure and removed from the laundry. Accordingly, the liquid carbon dioxide-based cleaning may be a cleaning method that needs no drying process.
  • liquid carbon dioxide-based cleaning mentioned above has several advantages but one disadvantage of insufficient cleaning power. That is because only liquid carbon dioxide-based cleaning fails to remove diverse contaminants (e.g., water-based or oil-based organic pollutants and inorganic contaminants).
  • laundry detergents applied to washing in water may not be dissolved in liquid carbon dioxide such that it cannot be suitable for the liquid carbon dioxide-based cleaning.
  • German company Kruessler uses additives such as Ethylene glycol so as to reinforce and improve such insufficient laundry cleaning power.
  • the laundry cleaning power is only slightly improved.
  • Cited document 1 PCT/US2000/13103 , published as WO 2000/070141
  • Embodiments of the present invention provide a liquid carbon dioxide based cleaning detergent composition having a new system.
  • Another object of the present invention is to provide a new liquid carbon dioxide based detergent composition having excellent cleaning efficiency for water-based contaminants as well as oil-based contaminants.
  • a further object of the present invention is to provide a new liquid carbon dioxide based cleaning detergent composition that has good friendliness with a non-polar solvent such as liquid carbon dioxide and water-based and oil-based contaminants removing substances so as to dissolve those contaminants removing substances in the liquid carbon dioxide easily.
  • a non-polar solvent such as liquid carbon dioxide and water-based and oil-based contaminants removing substances
  • a still further object of the present invention is to provide a new liquid carbon dioxide based cleaning composition that is safe for the human body and the environment and eco-friendly with no flammability.
  • Embodiments of the present invention may provide a liquid carbon dioxide based cleaning detergent composition including a fluorine based organic solvent that having excellent friendliness with a non-polar solvent such as liquid carbon dioxide and a polar element such as a contaminant remover.
  • the liquid carbon dioxide based cleaning detergent composition may include an organic solvent represented by Chemical formula 1; and a contaminant remover.
  • the liquid carbon dioxide based cleaning detergent composition may include the organic solvent represented by the following Chemical Formula 1, and various contaminant removing components may be sufficiently dissolved in a non-polar solvent such as liquid carbon dioxide.
  • Chemical Formula 1 R 1 -(CH 2 ) m (CR f F) n -R 2 wherein in chemical formula 1,
  • a preferred organic solvent expressed as chemical formula 1 is expressed as chemical formula 1a: [Chemical Formula 1a] R 1 -(CH 2 ) m (CF 2 ) n -R 2
  • 'm' represents an integer of from 0 to 4 and 'n' represents an integer of from 1 to 5.
  • 'R 1 ' and 'R 2 ' refer to hydrogen H, fluorine F, CH 3 , CH 3 Oor CF 3 .
  • 'R 1 ' and 'R 2 ' may be equal to or different from each other.
  • the liquid carbon dioxide based cleaning detergent composition may include a contaminant remover having excellent friendliness with the fluorine-based organic solvent represented by Chemical Formula 1, and the contaminant removing agent may be an oil-based contaminant removing agent represented by Chemical Formula 2 and it may include a water-based contaminant remover represented by Chemical Formula 3.
  • a contaminant remover having excellent friendliness with the fluorine-based organic solvent represented by Chemical Formula 1 may be an oil-based contaminant removing agent represented by Chemical Formula 2 and it may include a water-based contaminant remover represented by Chemical Formula 3.
  • 'm' refers to an integer of from 5 to 21 and 'n' refers to an integer of from 1 to 10.
  • liquid carbon dioxide-based cleaning detergent composition preferably controls the content of the organic solvent to 80% by weight or more in order to increase the solubility of the detergent composition in liquid carbon dioxide, and preferably includes 1 to 20% of a contaminant remover.
  • liquid carbon dioxide based cleaning detergent composition according to the present invention has a sufficient solubility to be dissolved in a non-polar solvent such as liquid carbon dioxide.
  • the liquid carbon dioxide based cleaning detergent composition according to the present invention may include an organic solvent for efficiently dissolving a contaminant remover that is a polar element in the a non-polar solvent such as liquid carbon dioxide. Accordingly, the liquid carbon dioxide based cleaning detergent composition may realize an excellent contaminant removing function, when applied to the liquid carbon dioxide based cleaning.
  • liquid carbon dioxide based cleaning detergent composition may provide a laundry cleaning environment that is safe for the human body and the environment and eco-friendly, with no flammability.
  • a singular representation may include a plural representation unless it represents a definitely different meaning from the context.
  • liquid carbon dioxide cleaning detergent composition is described.
  • Embodiments of the present invention relate to detergent composition having excellent usability for high-pressure liquid carbon dioxide cleaning, more particularly, to liquid carbon dioxide based cleaning detergent composition that may have excellent solubility of detergent ingredients in liquid carbon dioxide enough to efficiently remove both oil-based contaminants and water-based contaminants.
  • the liquid carbon dioxide based cleaning detergent composition according to the present invention includes an organic solvent represented by following Chemical Formula 1; and a contaminant remover.
  • the liquid carbon dioxide based cleaning detergent composition may include an organic solvent that is used in efficiently dissolving a contaminant remover, without phase-change of liquid carbon dioxide that might occur by pressure decrease in a tub.
  • the organic solvent according to the present invention is a fluorine solvent represented by following Chemical Formula 1: [Chemical Formula 1] R 1 -(CH 2 ) m (CR f F) n -R 2 wherein in chemical formula 1,
  • a preferred organic solvent expressed as chemical formula 1 is expressed as chemical formula 1a: [Chemical Formula 1a] R 1 -(CH 2 ) m (CF 2 ) n -R 2
  • 'm' represents an integer of from 0 to 4 and 'n' represents an integer of from 1 to 5.
  • 'R 1 ' and 'R 2 ' refer to hydrogen H, fluorine F, CH 3 , CH 3 O or CF 3 .
  • 'R 1 ' and 'R 2 ' may be equal to or different from each other.
  • the fluorine-based organic solvent may have excellent friendliness with generally polar and non-polar solvents and excellent mixing force with liquid carbon dioxide that is provided as a non-polar solvent in the tub.
  • the fluorine-base organic solvent may have excellent friendliness with organic solvents such as fiber-based, chlorine-based, cyclic silicone or silicone-based, fluorine-based, terpene oil-based organic solvents, and anionic and cationic surfactants or water-soluble raw materials.
  • the fluorine-based organic solvent according to the present invention may be provided to maintain a homogeneous phase of a raw material when the non-polar liquid carbon dioxide solvent is mixed with the contaminant remover.
  • the fluorine-base organic solvent may include one or more selected from Pofluoroheptane (PFH, CH 3 (CF 2 ) 5 CF 3 ), pentafluorobutane (PFB, CF 3 CH 2 CF 2 CH 3 ), decafluoropentane (DFP, CF 3 (CFH) 2 CF 2 CF 3 ) and methoxy nonafluorobutane (MNF, CH 3 O(CF 2 ) 3 CF 3 .
  • the present invention may not be limited thereto.
  • the composition according to the present invention may include the contaminant remover having excellent friendliness with the organic solvent.
  • the composition may include an oil-based contaminant remover and a water-based contaminant remover.
  • the water-based contaminant remover may include a compound that may be represented by following Chemical formula 2: [Chemical formula 2] R 3 -O-(CO)-O-R 4
  • 'R 3 ' and 'R 4 ' refer to C 1-4 alkyl groups. 'R 3 ' and 'R 4 ' may be equal to or different from each other.
  • the oil-based contaminant remover may include one or more of the groups that include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.
  • the present invention may not be limited thereto.
  • the water-based contaminant remover may include a compound that is represented by following Chemical formula 3: [Chemical formula 3] C m H 2m+1 -O-(CH 2 CH 2 O) n -H
  • the water-based contaminant remover may include one or more of the groups polyoxy ethylene dodecanyl ether, polyoxy ethalene tetra decanyl ether, polyoxy hexadecanyl ether and polyoxy ethylene hepta decanyl ether.
  • the present invention may not be limited thereto.
  • liquid carbon dioxide cleaning detergent composition according to one embodiment of the present invention will be described.
  • the liquid carbon dioxide cleaning detergent composition may include 80 to 99 wt% of the organic solvent and 1 to 20 wt% of the contaminant remover.
  • the contaminant remover includes 1 to 10 wt% of the oil-based contaminant remover and 1 to 10 wt% of the water-based contaminant remover, based on 100 wt% of the composition. It is to be understood that any amounts of components of the composition of the present invention given in wt% are relative to 100 wt% of the composition as a whole. It is to be understood that “wt%” and “% by weight” are used interchangeably herein.
  • the organic solvent may be included in an amount of 80 to 90 wt% (by weight) in the liquid carbon dioxide-based cleaning detergent composition.
  • the content of the organic solvent in the composition is less than 80 wt%, there may be a problem in maintaining a uniform phase because the additive raw materials such as the contaminant remover are not sufficiently mixed.
  • the oil-based contaminant remover is preferably included in the composition in an amount of 1 to 10 wt%. If the content of the oil-based contaminant remover in the composition is less than 1 wt%, there may be a problem in that the oil-based contaminant removal of the fiber is lowered, and if it exceeds 10 wt%, there may be problems such as phase separation during the preparation of the composition.
  • the water-based contaminant remover is included in the composition in an amount of 1 to 10 wt%. If the content of the water-based contaminant remover in the composition is less than 1 wt%, there may be a problem in that the water-based contaminant removing power from the fiber is lowered, and if it exceeds 10% by weight, the remover may remain on the surface of the fiber when drying after washing and there may be a problem that stains may occur.
  • the liquid carbon dioxide of the liquid carbon dioxide based cleaning detergent composition described above. If the detergent composition is less than 5% by weight based on 100% by weight of the total amount of the detergent composition and the liquid carbon dioxide, the detergent content in the liquid carbon dioxide may be insufficient, thereby reducing oil-based and water-based stain removal power. In addition, when the detergent composition exceeds 15% by weight, there may be a problem in that the raw material used for the detergent remains on the surface of the fiber during drying after washing, resulting in stains.
  • a liquid carbon dioxide based cleaning detergent composition was prepared by adding an oil-based contaminant remover and a water-based contaminant remover to an organic solvent and stirring until a transparent liquid was obtained at room temperature.
  • a specimen (Kimtech Paper and cotton/poly 50:50) was prepared, and the specimen was immersed in water-based contamination by dissolving 10 g of mixed coffee in 100 mL of hot water and oil-based contamination, which is a common automobile transmission oil, respectively. After that, a stained cloth was prepared by drying at 60° C for 2 hours 30 minutes. The stained cloth was washed for 10 minutes in a liquid carbon dioxide cleaning tank in which 11 wt% of the detergent composition according to Examples and Comparative Examples was diluted.
  • the washing rate was calculated by observing the reflectance before and after washing with a colorimeter (Minolta CR-300 Chroma-meter). At this time, the washing rate was calculated by the formula ((R W -R S )/(R O -R S ))X100(%), where Ro is the surface reflectance of the original fabric, Rs is the surface reflectance of the soiled fabric before washing, and Rw is the surface reflectance of the soiled fabric after washing. It means the surface reflectance of the contaminated cloth.
  • the calculated wash rates are shown in Table 2 below.
  • liquid carbon dioxide based cleaning detergent composition of the present invention prepared by adding a fluorine-based solvent, a water-based contaminant remover, and an oil-based decontaminant remover can effectively remove oily and aqueous contaminants present on the fiber surface.

Abstract

The present invention relates to a detergent composition having excellent usability for high-pressure liquid carbon dioxide cleaning, more particularly, a liquid carbon dioxide-based cleaning detergent composition that has excellent solubility of detergent components in liquid carbon dioxide and can excellently remove both oil-based and water-based contaminants

Description

    BACKGROUND Field of the Invention
  • The present invention relates to a detergent composition excellent in usability for liquid carbon dioxide based cleaning.
  • Description of the Related Art
  • Generally, washing that is a process for eliminating dirt or contaminants from textile or clothes may be divided into two categories.
  • In one washing method, a surfactant may be dissolved in water and the alkalinity of water may increase to remove dirt or contaminants from textile or clothes. Hence, the fabric or clothes may be rinsed, and dehydrated and dried. That is a normal washing method and usually uses a laundry detergent.
  • In the other washing method, water may be used in such the alkaline washing conditions and a physical force of a washing machine operated for a preset time period may be used. The second washing method may remove oily contaminants from fabric (e.g., wool, silk and other natural protein fiber, artificial silk fiber and acetate fiber) by means of petroleum-based, chlorine-based, glycol ester-based, cyclic silicone, silicone-based fluorine-based, terpene oil-based such as limonene (hereinafter, 'solvent'). Here, the fabric may be fiver that generates deformation in a surface and inside to lose luster, and deformation such as contraction or relaxation. Hence, the second method may remove the solvent from the clothes or fabric based on a physical method and dry them to volatilize the solvent. That second washing method may be usually called 'dry cleaning'.
  • The first washing method using a typical laundry detergent may require much water. Because of that, the first washing method has an excellent effect in removing watery contaminants but a limit to the removal of oily contaminants. In addition, fabric surface and fiber inside may be deformed by the alkaline washing conditions and long-term contact with water. Accordingly, luster of fibers could be lost and contraction or relaxation of fibers could occur disadvantageously.
  • Recently, neutral liquid detergents are commercially available to prevent the clothing damage or deformation caused by detergent bases. However, such neutral liquid detergents are also used by diluting in water and still have a disadvantage in that the deformation by means of water cannot be alleviated.
  • Next, the dry cleaning method has an excellent effect in removing oily contaminants. However, such the dry cleaning uses substances that are categorized into the ones harmful to human body and environment or raw materials with poor flammability and poor polymer stability. Because of that, the raw materials used in the dry cleaning might cause malfunction of washing equipment and a fire.
  • Accordingly, a lot of researching is conducted in order to develop safer, eco-friendly and energy-efficient laundry cleaning than the washing and dry cleaning.
  • Currently in the US and Europe may be being introduced a cleaning method using liquid carbon dioxide instead of various chemical raw materials used in the conventional washing in water and dry cleaning, as laundry cleaning method having eco-friendly and energy-efficient effect. Compared with the washing in water and dry cleaning, the washing method using liquid carbon dioxide may be relatively harmless to human body and environment. In addition, low temperature washing may be possible in the liquid carbon dioxide and energy efficiency may be quite high. As recycling liquid carbon dioxide after the washing process, laundry turnover may be increased advantageously.
  • Thus, the liquid carbon dioxide-based cleaning may wash, rinse and dry various types of clothes by means of phase change characteristics between gas and liquid of carbon dioxide quickly and without damage, and remove contaminant remnants from the clothes. In the liquid carbon-based cleaning, liquid carbon dioxide may wash and rinse clothes at high pressure. Liquid carbon dioxide contained in the laundry may be vaporized quickly at low pressure and removed from the laundry. Accordingly, the liquid carbon dioxide-based cleaning may be a cleaning method that needs no drying process.
  • The liquid carbon dioxide-based cleaning mentioned above has several advantages but one disadvantage of insufficient cleaning power. That is because only liquid carbon dioxide-based cleaning fails to remove diverse contaminants (e.g., water-based or oil-based organic pollutants and inorganic contaminants).
  • Research on detergents suitable for the liquid carbon dioxide-based cleaning is ongoing.
  • First of all, laundry detergents applied to washing in water may not be dissolved in liquid carbon dioxide such that it cannot be suitable for the liquid carbon dioxide-based cleaning.
  • Accordingly, there was an attempt to apply surfactants to the laundry detergent to dissolve the laundry detergent for washing in water into the liquid carbon dioxide. Prior art relating to a liquid carbon dioxide based cleaning ( PCT/US2000/13103 , published as WO 2000/070141 ) discloses that fluorine-based surfactants are used in detergent compositions for liquid carbon dioxide based cleaning. Even when such fluorine-based surfactants are used, laundry detergent is not sufficiently dissolved in carbon dioxide and a laundry washing power for water-based contaminants is not satisfactory.
  • In addition, the German company Kruessler uses additives such as Ethylene glycol so as to reinforce and improve such insufficient laundry cleaning power. However, the laundry cleaning power is only slightly improved.
  • The prior art mentioned above demands a connection medium that reacts carbon dioxide and surfactants. However, a solution that can react carbon dioxide and surfactants with each other is not yet known.
  • [Cited document]
  • Cited document 1: PCT/US2000/13103 , published as WO 2000/070141
  • SUMMARY
  • The invention is specified by the independent claims. Preferred embodiments are defined in the dependent claims.
  • Accordingly, an object of the present invention is to address the above-noted and other problems. Embodiments of the present invention provide a liquid carbon dioxide based cleaning detergent composition having a new system.
  • Another object of the present invention is to provide a new liquid carbon dioxide based detergent composition having excellent cleaning efficiency for water-based contaminants as well as oil-based contaminants.
  • A further object of the present invention is to provide a new liquid carbon dioxide based cleaning detergent composition that has good friendliness with a non-polar solvent such as liquid carbon dioxide and water-based and oil-based contaminants removing substances so as to dissolve those contaminants removing substances in the liquid carbon dioxide easily.
  • A still further object of the present invention is to provide a new liquid carbon dioxide based cleaning composition that is safe for the human body and the environment and eco-friendly with no flammability.
  • Aspects according to the present invention are not limited to the above ones, and other aspects and advantages that are not mentioned above can be clearly understood from the following description and can be more clearly understood from the embodiments set forth herein. Additionally, the aspects and advantages in the present invention can be realized via means and combinations thereof that are described in the appended claims.
  • Embodiments of the present invention may provide a liquid carbon dioxide based cleaning detergent composition including a fluorine based organic solvent that having excellent friendliness with a non-polar solvent such as liquid carbon dioxide and a polar element such as a contaminant remover.
  • The liquid carbon dioxide based cleaning detergent composition may include an organic solvent represented by Chemical formula 1; and a contaminant remover. The liquid carbon dioxide based cleaning detergent composition may include the organic solvent represented by the following Chemical Formula 1, and various contaminant removing components may be sufficiently dissolved in a non-polar solvent such as liquid carbon dioxide.

             [Chemical Formula 1]     R1-(CH2)m(CRfF)n-R2

    wherein in chemical formula 1,
    • 'm' represents an integer of from 0 to 4,
    • 'n' represents an integer of from 1 to 5,
    • 'Rf' represents hydrogen or fluorine, preferably fluorine,
    • 'R1' and 'R2' are selected from hydrogen, fluorine, CH3, CH3O and CF3, wherein 'R1'
    • and 'R2' may be equal to or different from each other.
  • A preferred organic solvent expressed as chemical formula 1 is expressed as chemical formula 1a:

             [Chemical Formula 1a]     R1-(CH2)m(CF2)n-R2

  • In Chemical formula 1a, 'm' represents an integer of from 0 to 4 and 'n' represents an integer of from 1 to 5. 'R1' and 'R2' refer to hydrogen H, fluorine F, CH3, CH3Oor CF3. 'R1' and 'R2' may be equal to or different from each other.
  • It is to be understood that any reference herein to chemical formula 1 also represents a reference to any preferred definitions of chemical formula 1, such as chemical formula 1a.
  • The liquid carbon dioxide based cleaning detergent composition may include a contaminant remover having excellent friendliness with the fluorine-based organic solvent represented by Chemical Formula 1, and the contaminant removing agent may be an oil-based contaminant removing agent represented by Chemical Formula 2 and it may include a water-based contaminant remover represented by Chemical Formula 3.

             [Chemical formula 2]     R3-O-(CO)-O-R4

  • In Chemical formula 2, 'R3' and 'R4' refer to C1-4 alkyl groups. 'R3 and 'R4' may be equal to or different from each other.

             [Chemical formula 3]     CmH2m+1-O-(CH2CH2O)n-H

  • In Chemical formula 3, 'm' refers to an integer of from 5 to 21 and 'n' refers to an integer of from 1 to 10.
  • In addition, the liquid carbon dioxide-based cleaning detergent composition preferably controls the content of the organic solvent to 80% by weight or more in order to increase the solubility of the detergent composition in liquid carbon dioxide, and preferably includes 1 to 20% of a contaminant remover.
  • Accordingly, the liquid carbon dioxide based cleaning detergent composition according to the present invention has a sufficient solubility to be dissolved in a non-polar solvent such as liquid carbon dioxide.
  • In addition, the liquid carbon dioxide based cleaning detergent composition according to the present invention may include an organic solvent for efficiently dissolving a contaminant remover that is a polar element in the a non-polar solvent such as liquid carbon dioxide. Accordingly, the liquid carbon dioxide based cleaning detergent composition may realize an excellent contaminant removing function, when applied to the liquid carbon dioxide based cleaning.
  • In addition, the liquid carbon dioxide based cleaning detergent composition may provide a laundry cleaning environment that is safe for the human body and the environment and eco-friendly, with no flammability.
  • Further scope of applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given as illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
  • DETAILED DESCRIPTION
  • The above-described aspects, features and advantages are specifically described hereunder such that one having ordinary skill in the art to which the present invention pertains can easily implement the technical spirit of the invention. In the invention, detailed descriptions of known technologies in relation to the invention are omitted if they are deemed to make the gist of the invention unnecessarily vague. Below, preferred embodiments according to the invention are specifically described.
  • A singular representation may include a plural representation unless it represents a definitely different meaning from the context.
  • Terms such as "include" or "has" are used herein and should be understood that they are intended to indicate an existence of several components, functions or steps, disclosed in the specification, and it is also understood that greater or fewer components, functions, or steps may likewise be utilized.
  • Hereinafter, liquid carbon dioxide cleaning detergent composition is described.
  • Embodiments of the present invention relate to detergent composition having excellent usability for high-pressure liquid carbon dioxide cleaning, more particularly, to liquid carbon dioxide based cleaning detergent composition that may have excellent solubility of detergent ingredients in liquid carbon dioxide enough to efficiently remove both oil-based contaminants and water-based contaminants.
  • The liquid carbon dioxide based cleaning detergent composition according to the present invention includes an organic solvent represented by following Chemical Formula 1; and a contaminant remover.
  • First of all, the organic solvent provided in the liquid carbon dioxide based cleaning detergent composition will be described. The liquid carbon dioxide based cleaning detergent composition may include an organic solvent that is used in efficiently dissolving a contaminant remover, without phase-change of liquid carbon dioxide that might occur by pressure decrease in a tub. The organic solvent according to the present invention is a fluorine solvent represented by following Chemical Formula 1:

             [Chemical Formula 1]     R1-(CH2)m(CRfF)n-R2

    wherein in chemical formula 1,
    • 'm' represents an integer of from 0 to 4,
    • 'n' represents an integer of from 1 to 5,
    • 'Rf' represents hydrogen or fluorine, preferably fluorine,
    • 'R1' and 'R2' are selected from hydrogen, fluorine, CH3, CH3O and CF3, wherein 'R1' and 'R2' may be equal to or different from each other.
  • A preferred organic solvent expressed as chemical formula 1 is expressed as chemical formula 1a:

             [Chemical Formula 1a]     R1-(CH2)m(CF2)n-R2

  • In Chemical formula 1a, 'm' represents an integer of from 0 to 4 and 'n' represents an integer of from 1 to 5. 'R1' and 'R2' refer to hydrogen H, fluorine F, CH3, CH3O or CF3. 'R1' and 'R2' may be equal to or different from each other.
  • The fluorine-based organic solvent may have excellent friendliness with discursive polar and non-polar solvents and excellent mixing force with liquid carbon dioxide that is provided as a non-polar solvent in the tub. In addition, the fluorine-base organic solvent may have excellent friendliness with organic solvents such as fiber-based, chlorine-based, cyclic silicone or silicone-based, fluorine-based, terpene oil-based organic solvents, and anionic and cationic surfactants or water-soluble raw materials.
  • Accordingly, the fluorine-based organic solvent according to the present invention may be provided to maintain a homogeneous phase of a raw material when the non-polar liquid carbon dioxide solvent is mixed with the contaminant remover.
  • Specifically, the fluorine-base organic solvent may include one or more selected from Pofluoroheptane (PFH, CH3(CF2)5CF3), pentafluorobutane (PFB, CF3CH2CF2CH3), decafluoropentane (DFP, CF3(CFH)2CF2CF3) and methoxy nonafluorobutane (MNF, CH3O(CF2)3CF3. The present invention may not be limited thereto.
  • Next, the contaminant remover provided in the liquid carbon dioxide based cleaning detergent composition will be described.
  • The composition according to the present invention may include the contaminant remover having excellent friendliness with the organic solvent. Specifically, the composition may include an oil-based contaminant remover and a water-based contaminant remover.
  • The water-based contaminant remover may include a compound that may be represented by following Chemical formula 2:

             [Chemical formula 2]     R3-O-(CO)-O-R4

  • In Chemical formula 2, 'R3' and 'R4' refer to C1-4 alkyl groups. 'R3' and 'R4' may be equal to or different from each other.
  • Next, the oil-based contaminant remover provided in the composition according to the present invention will be described.
  • Specifically, the oil-based contaminant remover may include one or more of the groups that include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate. The present invention may not be limited thereto.
  • Next, the water-based contaminant remover may include a compound that is represented by following Chemical formula 3:

             [Chemical formula 3]     CmH2m+1-O-(CH2CH2O)n-H

  • In Chemical formula 3, 'm' represents an integer of from 5 to 21 and 'n' represents an integer of from 1 to 10.
  • Specifically, the water-based contaminant remover may include one or more of the groups polyoxy ethylene dodecanyl ether, polyoxy ethalene tetra decanyl ether, polyoxy hexadecanyl ether and polyoxy ethylene hepta decanyl ether. The present invention may not be limited thereto.
  • Next, the liquid carbon dioxide cleaning detergent composition according to one embodiment of the present invention will be described.
  • The liquid carbon dioxide cleaning detergent composition according to one embodiment may include 80 to 99 wt% of the organic solvent and 1 to 20 wt% of the contaminant remover.
  • Preferably, the contaminant remover includes 1 to 10 wt% of the oil-based contaminant remover and 1 to 10 wt% of the water-based contaminant remover, based on 100 wt% of the composition. It is to be understood that any amounts of components of the composition of the present invention given in wt% are relative to 100 wt% of the composition as a whole. It is to be understood that "wt%" and "% by weight" are used interchangeably herein.
  • First of all, the organic solvent may be included in an amount of 80 to 90 wt% (by weight) in the liquid carbon dioxide-based cleaning detergent composition.
  • When the content of the organic solvent in the composition is less than 80 wt%, there may be a problem in maintaining a uniform phase because the additive raw materials such as the contaminant remover are not sufficiently mixed.
  • Next, the oil-based contaminant remover is preferably included in the composition in an amount of 1 to 10 wt%. If the content of the oil-based contaminant remover in the composition is less than 1 wt%, there may be a problem in that the oil-based contaminant removal of the fiber is lowered, and if it exceeds 10 wt%, there may be problems such as phase separation during the preparation of the composition.
  • Next, the water-based contaminant remover is included in the composition in an amount of 1 to 10 wt%. If the content of the water-based contaminant remover in the composition is less than 1 wt%, there may be a problem in that the water-based contaminant removing power from the fiber is lowered, and if it exceeds 10% by weight, the remover may remain on the surface of the fiber when drying after washing and there may be a problem that stains may occur.
  • On the other hand, it is preferable to contain 5 to 15% by weight in the liquid carbon dioxide of the liquid carbon dioxide based cleaning detergent composition described above. If the detergent composition is less than 5% by weight based on 100% by weight of the total amount of the detergent composition and the liquid carbon dioxide, the detergent content in the liquid carbon dioxide may be insufficient, thereby reducing oil-based and water-based stain removal power. In addition, when the detergent composition exceeds 15% by weight, there may be a problem in that the raw material used for the detergent remains on the surface of the fiber during drying after washing, resulting in stains.
  • Hereinafter, one exemplary embodiment of the present invention will be described in detail.
  • [Embodiment] 1. Preparation of exemplary embodiments and comparative examples:
  • A liquid carbon dioxide based cleaning detergent composition was prepared by adding an oil-based contaminant remover and a water-based contaminant remover to an organic solvent and stirring until a transparent liquid was obtained at room temperature.
  • The components and compositions of the organic solvent, the contaminant remover, and the water-based contaminant remover are shown in Table 1 below. [Table 1]
    Category Organic solvent (wt%) Oil-based contaminant remover (wt%) Water-based contaminant remover (wt%)
    A1 A2 A3 A4 B1 B2 B3 B4 C1 C2 C3 C4
    Embodiment 1 89 1 10
    Embodiment 2 85 5 10
    Embodiment 3 80 10 10
    Embodiment 4 89 10 1
    Embodiment 5 90 5 5
    Embodiment 6 89.5 0.5 10
    Embodiment 7 89.5 10 0.5
    Embodiment 8 75 10 15
    Embodiment 9 89 1 10
    Embodiment 10 85 5 10
    Embodiment 11 80 10 10
    Embodiment 12 89 10 1
    Embodiment 13 90 5 5
    Embodiment 14 89.5 0.5 10
    Embodiment 15 89.5 10 0.5
    Embodiment 16 75 10 15
    Embodiment 17 89 1 10
    Embodiment 18 85 5 10
    Embodiment 19 80 10 10
    Embodiment 10 89 10 1
    Embodiment 21 90 5 5
    Embodiment 22 89.5 0.5 10
    Embodiment 23 89.5 10 0.5
    Embodiment 24 75 10 15
    Embodiment 25 89 1 10
    Embodiment 26 85 5 10
    Embodiment 27 80 10 10
    Embodiment 28 89 10 1
    Embodiment 29 90 5 5
    Embodiment 30 89.5 0.5 10
    Embodiment 31 89.5 10 0.5
    Embodiment 32 75 10 15
    A1: pentafluorobutane
    A2: perfluoroheptane
    A3: decafluoropentane
    A4: methoxy nonafluorobutane
    B1: dimethyl carbonate
    B2: diethyl carbonate
    B3: dipropyl carbonate
    B4: dibutyl carbonate
    C1: polyoxyethylene(7) dodecyl ether
    C2: polyoxy ethylene tetradecanyl ether
    C3: polyoxy hexadecanyl ether
    C4: polyoxyethylene hepta decanyl ether
  • Comparative Example 1: Electrolux detergent composition Comparative Example 2: Professional wet cleaning Comparative Example 3: Professional dry cleaning 2. Washing performance evaluation
  • A specimen (Kimtech Paper and cotton/poly 50:50) was prepared, and the specimen was immersed in water-based contamination by dissolving 10 g of mixed coffee in 100 mL of hot water and oil-based contamination, which is a common automobile transmission oil, respectively. After that, a stained cloth was prepared by drying at 60° C for 2 hours 30 minutes. The stained cloth was washed for 10 minutes in a liquid carbon dioxide cleaning tank in which 11 wt% of the detergent composition according to Examples and Comparative Examples was diluted.
  • After washing, the washing rate was calculated by observing the reflectance before and after washing with a colorimeter (Minolta CR-300 Chroma-meter). At this time, the washing rate was calculated by the formula ((RW-RS)/(RO-RS))X100(%), where Ro is the surface reflectance of the original fabric, Rs is the surface reflectance of the soiled fabric before washing, and Rw is the surface reflectance of the soiled fabric after washing. It means the surface reflectance of the contaminated cloth. The calculated wash rates are shown in Table 2 below.
  • In addition, after leaving each of the detergent composition stock solutions according to Examples and Comparative Examples under severe conditions (50°C. oven and -5°C incubator, 7 days), the phase separation phenomenon and transparency of the detergent composition stock solution were visually observed and evaluated. After 7 days, the degree of suspension and separation of the detergent stock solution was evaluated as good or bad, and if the phase of the detergent stock solution was transparent without change, it was marked as excellent.
  • The performance evaluation and phase stability evaluation results are shown in Table 2 below. [Table 2]
    category Phase stability (50°C) Phase stability (-15°C) flammabili ty Washing rate(%)
    Water-based contamina nt Oil-based contamina nt
    Embodiment 1 Excellent Excellent Excellent >80 >90
    Embodiment 2 Excellent Excellent Excellent >80 >90
    Embodiment 3 Excellent Excellent Excellent >80 >90
    Embodiment 4 Excellent Excellent Excellent >80 >90
    Embodiment 5 Excellent Excellent Excellent >80 >90
    Embodiment 6 Excellent Excellent none >80 <60
    Embodiment 7 Excellent Excellent none <60 >90
    Embodiment 8 Good Good none >80 >90
    Embodiment 9 Excellent Excellent none >80 >90
    Embodiment 10 Excellent Excellent none >80 >90
    Embodiment11 Excellent Excellent none >80 >90
    Embodiment 12 Excellent Excellent none >80 >90
    Embodiment 13 Excellent Excellent none >80 >90
    Embodiment 14 Excellent Excellent none >80 <60
    Embodiment 15 Excellent Excellent none <60 >90
    Embodiment 16 Good Good none >80 >90
    Embodiment 17 Excellent Excellent none >80 >90
    Embodiment 18 Excellent Excellent none >80 >90
    Embodiment 19 Excellent Excellent none >80 >90
    Embodiment 20 Excellent Excellent none >80 >90
    Embodiment 21 Excellent Excellent none >80 >90
    Embodiment 22 Excellent Excellent none >80 <60
    Embodiment 23 Excellent Excellent none <60 >90
    Embodiment 24 Good Good none >80 >90
    Embodiment 25 Excellent Excellent none >80 >90
    Embodiment 26 Excellent Excellent none >80 >90
    Embodiment 27 Excellent Excellent none >80 >90
    Embodiment 28 Excellent Excellent none >80 >90
    Embodiment 29 Excellent Excellent none >80 >90
    Embodiment 30 Excellent Excellent none >80 <60
    Embodiment 31 Excellent Excellent none <60 >90
    Embodiment 32 Good Good none >80 >90
    Comparative example 1 Excellent Excellent none <10 <70
    Comparative example 2 Excellent Excellent none >90 <10
    Comparative example 3 Excellent Excellent none <50 >90
  • From the above results, it was confirmed that the liquid carbon dioxide based cleaning detergent composition of the present invention prepared by adding a fluorine-based solvent, a water-based contaminant remover, and an oil-based decontaminant remover can effectively remove oily and aqueous contaminants present on the fiber surface.
  • In addition, in Examples 6 to 8, 14 to 16, 22 to 24, and 30 to 32, it can be seen that the content ratio of the organic solvent and the contaminant remover is not appropriate, so that the cleaning performance is slightly worse than in the other examples.
  • In addition, it can be seen that commercially available detergent compositions for cleaning liquid carbon dioxide have very poor ability to remove water-based contaminants.
  • The embodiments are described above with reference to a number of illustrative embodiments thereof. However, the present invention is not intended to limit the embodiments set forth herein, and numerous other modifications and embodiments can be devised by one skilled in the art. Further, the effects and predictable effects based on the configurations in the invention are to be included within the range of the invention though not explicitly described in the description of the embodiments.

Claims (13)

  1. A composition comprising:
    a contaminant remover, and
    an organic solvent represented by the following chemical formula 1:

             R1-(CH2)m(CRfF)n-R2     (1)

    wherein in chemical formula 1,
    'm' represents an integer of from 0 to 4,
    'n' represents an integer of from 1 to 5,
    'Rf' represents hydrogen or fluorine, preferably fluorine,
    'R1' and 'R2' are selected from hydrogen, fluorine, CH3, CH3O and CF3, wherein 'R1' and 'R2' may be equal to or different from each other.
  2. The composition of claim 1, wherein the organic solvent comprises one or more selected from Pofluoroheptane (PFH, CH3(CF2)5CF3), pentafluorobutane (PFB, CF3CH2CF2CH3), decafluoropentane (DFP, CF3(CFH)2CF2CF3) and methoxy nonafluorobutane (MNF, CH3O(CF2)3CF3).
  3. The composition of claim 1 or 2, wherein the contaminant remover comprises,
    an oil-based contaminant remover; and/or
    a water-based contaminant remover.
  4. The composition of claim 3, wherein the oil-based contaminant remover is represented by the following chemical formula 2:

             R3-O-(CO)-O-R4     (2)

    wherein, in chemical formula 2, 'R3' and 'R4' are each a C1-4 alkyl group, wherein 'R3 and 'R4' may be equal to or different from each other.
  5. The composition of claim 3 or 4, wherein the oil-based contaminant remover comprises one or more selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, and dibutyl carbonate.
  6. The composition of any one of claims 3 to 5, wherein the water-based contaminant remover is represented by the following chemical formula 3:

             CmH2m+1-O-(CH2CH2O)n-H     (3)

    wherein, in chemical formula 3, 'm' represents an integer of from 5 to 21, preferably from 10 to 18, and 'n' represents an integer of from 1 to 10.)
  7. The composition of any one of claims 3 to 6, wherein the water-based contaminant remover comprises one or more selected from polyoxy ethylene dodecanyl ether, polyoxy ethylene tetradecanyl ether, polyoxy hexadecanyl ether and polyoxy ethylene heptadecanyl ether.
  8. The composition of any one of claims 1 to 7, comprising:
    80 to 99 wt% of the organic solvent; and
    1 to 20 wt% of the contaminant remover.
  9. The composition of any one of claims 1 to 8, comprising:
    80 to 90 wt% of the organic solvent;
    1 to 10 wt% of the oil-based contaminant remover; and
    1 to 10 wt% of the water-based contaminant remover.
  10. The composition according to any one of claims 1 to 9, wherein the composition is a liquid carbon dioxide-based cleaning detergent composition.
  11. Use of the composition according to any of claims 1 to 10 as a detergent composition, preferably for liquid carbon dioxide-based cleaning.
  12. A method of cleaning using liquid carbon dioxide, including a step of using the composition according to any of claims 1 to 10.
  13. The use according to claim 11 or the method according to claim 12, wherein the cleaning is laundry cleaning.
EP21217805.7A 2020-12-28 2021-12-27 Detergent composition for liquid carbon dioxide based cleaning Pending EP4019617A1 (en)

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Citations (3)

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WO2000070141A1 (en) 1999-05-14 2000-11-23 Micell Technologies, Inc. Detergent injection systems for carbon dioxide cleaning apparatus
US6846790B2 (en) * 2001-10-26 2005-01-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dry cleaning process comprising a non-aqueous step and a low aqueous step
CN107858215A (en) * 2017-11-30 2018-03-30 兰秋波 Culinary cleaning agent

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JPH06212195A (en) * 1993-01-19 1994-08-02 San Seal:Kk Solvent for dry cleaning
US5858022A (en) * 1997-08-27 1999-01-12 Micell Technologies, Inc. Dry cleaning methods and compositions
JP3941013B2 (en) * 2003-09-10 2007-07-04 第一工業製薬株式会社 Cleaning composition for dry cleaning
KR101224444B1 (en) * 2006-04-17 2013-01-21 주식회사 엘지생활건강 Solid/liquid phase transfer type laundry detergent
KR20180081995A (en) * 2017-01-09 2018-07-18 엘지전자 주식회사 Dry Cleansing Composition

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WO2000070141A1 (en) 1999-05-14 2000-11-23 Micell Technologies, Inc. Detergent injection systems for carbon dioxide cleaning apparatus
US6846790B2 (en) * 2001-10-26 2005-01-25 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Dry cleaning process comprising a non-aqueous step and a low aqueous step
CN107858215A (en) * 2017-11-30 2018-03-30 兰秋波 Culinary cleaning agent

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